Dye of the anthracene series and process of making same.



UNITED STATES ATENT MAX HENRY ISLER, OF MANNHEIM, GERMANY, ASSIGNOR TOBADISOHE ANILIN dz SODA FABRIK, OF LUDWIGSHAFEN, GERMANY, A CORPORA-TION OF BADEN. t

DYE OF THE ANTHRACENE SERIES AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 688,645, dated December10, 1901.

Application filed August 13, 1901. Serial No. 71,958. (No specimens.)

To all whom it may concern.-

Be it known that 1, MAX HENRY ISLER, chemist, a citizen of the SwissRepublic, residing at Mannheim, in the Grand Duchy of Baden, in theEmpire of Germany, have invented new and useful Improvements in C01-oring-Matters of the Anthracene Series and Processes of Producing theSame, of which the following is a specification.

It is known that halogen-substituted amido-ant-hraquinones and theirderivatives are capable of being condensed with primary aromatic aminsto form substances which in a sulfonated state are valuablecoloring-matters. The condensation is in general brought about byheating with an aromatic amin for a sufficient length of time thehalogenized 'an thraquinone substance chosen with or without a solventor diluent, as the circumstances may require. If the melt thus obtained(for example, when para-toluidin is employed) be worked up by treatingit directly with dilute hydrochloric acid, an impure coloring-matter, asa rule, separates out, which is either Worthless or must be furtherpurified. It is therefore preferable to treat the melt (in which, forexample, para-toluidin is the amin used) with alcohol and to collect theundissolved coloring-matter by filtration, as then a large amount of theimpurities remains dissolved in the alcohol. I have discovered that bycarrying on the condensation with the addition of a substance acting asa weak alkali coloring-matters can be obtained which in the form oftheir sulfo-acids dye wool shades different from and more brilliant andclearer than those of the sulfonated coloring-matters produced by thecondensation of halogenamido-anthraquinone substances and aromatic aminswithout the aid of a substance acting as a Weak alkali.

I have found sodium carbonate and sodium acetate (more especially thelatter) suitable j substances for use for the purposes of my invention;but other compounds can also be used, and the addition of thesesubstances to r the melt, which at times delays the com mencement of thereaction, appears to exercise a protective and favorable influence onthe progress of the reaction. This influence is more or less marked,according to the halogen-substituted inonoor diamido-anthraquinonesubstance employed, and is very striking in the condensation of aromaticamins with halogenmono-amido-2-Inethyl-an- ,thraquinone andhalogen-diamido-Z-methylanthraquinone, (see application for LettersPatent, Serial No. 40,443, dated December 19, 1900,) halogen mono amidoanthraquinone, (see the specifications of Patents Nos. 654,294 and651,295,) and halogen-diamidoant-hraquinones. (See the specifications ofLetters Patents Nos. 631,607 and 631,608.)

In this application I wish to claim the new coloring-matter frommono-amido-2-methylanthraquinone bromid and an aromatic amin, such ascan be obtained in accordance with Example 1, as hereinafter explained,and my improved process of producing the abovementioned coloring-mattersin general with the aid of a substance acting as a weak alkali.

My new coloring-matter in the form of its sulfo-acid dissolves in water,yielding a violet-blue solution. Thin layers of its solution inconcentrated sulfuric acid (containing about ninety-six per cent. of H80 appear blue-Violet. Its solution in warm concentrated sulfuric acidto which boric acid has been added is blue with a red fluorescence. Itssolution in anilin is blue and it dyes unmordanted wool pure blueshades.

The following examples will serve to further illustrate the nature of myinvention and the manner in which the same may be carried into practicalelfect; but the invention is not confined to these examples. The partsare by weight.

Example 1;: Boil in a reflux apparatus for about three (3) hours ten(10) parts of monoamido-2-methyl-anthraquinone bromid, (see theapplication for Letters Patent, Serial No. 40,443, dated December 19,1900,) one hundred (100) parts of para-toluidin, and ten (10) parts ofanhydrous sodium acetate. The melt assumesamagnificent violet-bluecolor. Pour it into an excess of dilute hydrochloric acid, collect thecoloring-matter, which separates out by filtration, wash and dry it. Inits sulfonated form it dyes unmordanted Wool brilliant blue shades,while the coloring-matter obtained in a similar manner but without theuse of acetate dyes dull grayish shades.

By employing sodium carbonate in place of sodium acetate the resultingdyestuff is more brilliant than that obtained without the use of either;but the improvement in this respect is not so great as that occasionedby acetate. When using sodium carbonate, the ingredients should not beboiled for more than about one and a half (1 1 hours or until a testportion shows that the maximum yield of coloring-matter has beenobtained. In the same way other acetates-for example, leadacetate-exercise a favorable influence on the reaction.

Instead of the mono-a1nido-2-methyl-authraquiuone-bromid,chlor-amido-2-methylanthraquinone can be employed in the above examplewith similar results. It can be obtained, for instance, by treating onemolecular proportion of mouoarnido-2-methyl-anthraquinone with twoatomic proportions of chlorin in a chloroform solution or suspension.

Example 2: Boil in a reflux apparatus for from two (2) to three (3)hours ten (10) parts of brominated mono-amido-anthraquinone,

(obtainable as set forth in the specification of Letters Patent SerialNo. 654,294,) one hundred (100) parts of para-toluidin, and ten (10)parts of anhydrous sodium acetate, and work up the melt as described inthe foregoing example. In the sulfonated form the coloringmatter thusobtained dyes wool shades which ,of Letters Patents Nos. 631,607 and631,608

or of one of the halogen-diamido-Z-methyl-anthraquinones of thespecification of the application for Letters Patent, Serial No. 40,443,dated December 19, 1900. The sulfonation of these substances can beeffected in the known manner.-

Now what I claim is 1. The process of producing coloring-matters of theauthracene series by condensing the hereinbefore-definedhalogen-substituted anthraquinone substances with aromatic amins in thepresence of a substance acting as v solution in concentrated sulfuricacid appear blue-violet, whose solution in warm concentrated sulfuricacid to which boric acid has been added is blue with a red fluorescence,whose solution in anilin is .blue and which dyes unmordanted wool blueshades, substantially as described.

4. The new coloring-matter of the anthracene series such as can beobtained by condensing mono -.amido- 2 methyl anthraquinone-bromid withpara-toluidin in the presence of sodium acetate, which in thesulfona'ted form dissolves in water yielding a violet-blue solution,thin layers of whose solution in concentrated sulfuric acid appearblue-violet, whose solution in warm concentrated sulfuric acid to whichboric acid has been added is blue with a red fluorescence, whosesolution in anilin is blue and which dyes unmordanted wool blue shades,substantially as described.

In testimony whereof I have hereunto set my hand in the presence of twosubscribing witnesses.

MAX HENRY ISLER. Witnesses:

JOHN L. HEINKE, JAooB ADRIAN.

